Production of olefines and liquid hydrocarbons from methane



Nov. 26, 1935. ZR'F ILER 2,022,279

PRODUCTION OF OLEFINES AND LIQUliD HYDROCARBONS FROM METHANE Filed Feb. ;16, 1951 Ham l zs 607.67g anvemtow l Paul Hiler 33 his 6mm Pa ed e -$1 9 f l V 24 721 UNITED sures/ ATENT OFFICE- 2,022,219

monucrion or OLEFINES AND LIQUID maocsnnons mom m-i'rnann.

Paul- Feller, Ludtvigshafen-on-the-Rhine, Gerassignor to I. G. Farbenindustrie Aktien gesellschalt, i ranklort-on-the-Main, Germany Application man-y is, 1931, Serial No. 515,912

' "In Germany February 28, 1930 i chm, (circa-11o) The present invention relates to the productures of between 1200 and 1300 C. are very tion of oleflnes and liquid, more especially arosuitable; L matic hydrocarbons, which are hereinafter re- Wh a n a as m tu e co pr n bot ferred to for the sake of brevity as hydrocarbons methane and its higher homologues, such as containing double bonds in the molecule, from ethane, propane and butane it is preferable first 5 methane. to treat the said gas mixture at temperatures be- I have found that particularly high yields of low 900 C., for example at between 700 and 900 hydrocarbons containing double bonds in the C. and then in a second stage, after the removal molecule are obtained by. thermally treating of the hydrocarbons containing double bonds methane or a gas comprising methane in the in the molecule produced, totreat the residual gas 10- presence of a material comprising silicon carbide. 'a temp ra ures of between 900 and 1300 C. The said material comprising silieon carbide This method of working is employed because the may be employed fonthe construction of the aphomologues of methane are' converted at temparatus' or as a filling'material f r the a a peratures of between 700 and 900 C. in accord- 15 tus, For example, tubes, shaft furnaces or ance with the present invention into hydrocar: 15 bowpersmay be constructed of the said material. h n containing d ble b nds in the m lecule. A material comprising silicon carbide may in parwhereas at higher temperatures an undesirable ticular beemployed 'for constructing the heat Production carbon, yd and methane regenerators in the said Cowper apparatus. takes place. On the other hand methane is not Among t materials cgmpflsing i o a converted at temperatures lower than 900 C. in 20 bide coming 'into question in a rdan ith substantial amounts into products of the nature the present invention may be mentioned in the obta n d in accordance w th h p e ent venfirst place; silicon carbide itself 'or a material tiOn.

containing more than 20 per cent and preferably T e Process in aeeelfdence with the present more tha 604 per nt of ili on arbid U u linvention is'carried outwith patricular advantage 25 ly the materials employed will contain between by Operating!!! e chamber n r ct d f a m p 60 and 95 per cent of silicon carbide, The reteriai comprising silicon carbide and filled with mainder consists of binding agents amo hi h chequer work of the same material and alternatethose readily melting, such as :[eldgpars d 15* heating up the said chequerwork to the decryolites or other readily melting silicates or r d mp rature of between about 900 and 30 fluor spar, have proved to be particularly advan- 1300 C. by passing hot gases, such as hot comtageous.- g bustion gases or hot producer gas therethrough,

Among the gases to be treated according to n fpa ins methane or ga p i i the present invention may be mentioned methane methane il the chambers thus heated pu e]! or gas i t containing m t f such The process according to the present invention 35 as mixtures thereof with homologues of methane, is usually carried out a m ph ri r li y such as ethane or propane or butane, or natural elevated n e- Higher Pressures. are also gas, coke ovengas r th gases obtained by vantageous where'pressure-resistant apparatus is degasiflcation of rbo materials, crack. .a available, since in this manner a higher through-v ing gases or waste gases of the destructive hy- Put isoattameddmgenation f carbonaceous matema The .It has been found advantageous" to work with methane fractions obtained by the fractionation 3 i g of the gases that g mix me ane is on ypar 1a y ecompose since in is v or such hues may also be employed In mannerthe formation of soot and of hydrogen an case the initial gases should contain at least is suppressed in a marked degree. The methane 45 20 per cent of methane.

' contained in the residual gas is preferably ref zi' r g accordance with covered by scr ibbing said gas with a mineral or e presen on y carried out at tar oil under pressure and is then again subjected temperatures of between 900 and 1300 C. The to the said treatment '50 hi the eenentmtmn methane in e In order to have an eflicient heat economy the itial'ga the lower i the temperature fresh gases are preferably passed in counter-cur- Thu if the 8 contains m r than rent to the efliuent reaction gases. In ,the heat :per cent of methane temperatures of between, exchange apparatus employed for this purpose about 1000? and 1100 C. are very suitable for the temperatureis usually maintained so low that i the com lersion.v with more dilute gases temperairon may be employed for the construction of the 5 said exchange apparatus. The said principle of heat exchange may be applied with particular advantage when working with several chambers ed in series. v

The following example which is with reference to the accompanying drawing will further illustrate how the said invention may be carried out in practice but it should be understood that the invention is not limited to the said example nor to operations carried out in the specific type of apparatus illustrated.

The drawing shows diagrammatically in elevatlon and partly in section a Cowper for a treatment of gases comprising methane.

Referring to the drawing, the Cowper has a height from K to L of 6.25 meters and the chequer work B consists of 400 kilograms of a material containing 90 per cent of silicon carbide, the remainder being a binding agent of feldspathic nature. The said material is periodically heated up to a temperature of about 1100 C. by burning in the chamber A producer gas introduced thereinto by means of the pipe F with the aid of an oxygen-bearing gas introduced by way of the pipe G. The hot gases oi! combustion passL- ofl at C, the valves J and M being kept closed. After each heating period the valve H is closed :and

' the valves J and M are opened and a gas comprising 90 per cent of methane is introduced at D. In all 15 cubic meters of the said gas comprising methane are passed through hourly. The reaction products are withdrawn at E and contain after a single passage for each cubic meter of the initial gas passed through grams of a condensate to the extent" of about .45 per, cent of benzene, about 12 per cent of toluene.

xylene and alkyl naphthalenes, the remainder consisting mainly of naphthalene. The residual In the conversion of a gas essentially comprising methane and its higher homologues into oleflnes and aromatic hydrocarbons, the steps of alternately heating by heat regeneration in a Cow- 20 per furnace a refractory material comprising'between and of silicon carbide, the remainder being a binding agent of feldspathic nature selected from the class consisting of feldspars,

cryolites, and fluorspars to a temperature be- 5 tween '100and 900 C., contacting said gas with said heated refractory material, removing the unsaturates formed, alternately heating by heat regeneration said refractory material to a temperature between 900 and 1300 C. and contact- 3 ing the residual gas with said heated refractory material.

PAUL FEILER. 

